Detergent



40 produced f relatively inexpensive art n able cation, for example, potassium, am 40 Patented June 11,1940 I v I UNITED, STATES PATENT OFFICE DETERGENT Fred Weaver Muncie, New Brunswick, N. 1., and Kenneth L. Russell, New York, N. 1., asslgnors to Colgate-Palmoliv -Peet Company, Jersey City, N. .L, a corporation of Delaware No Drawing. Application January is, 1938,

Serial No. 185,622

' 13 Claims. (Cuzco-400i This invention relates to certain new chem- By following the principles of the present inical compositions and a method for their preparavention, the use of g'lycerine is avoided, a product tion. a The compositions are particularly useful being substituted therefor that functions excepas wetting agents, foaming agents, detergents tionallywell for the present purpose, but which 5 and emulsiflers in treating textiles, in floating has not been found satisfactory for use in ex- 5 ores, as ingredients in laundry and textile plosives, and which, as a consequence, is much preparations, and for many other purposes.- -cheaper than glycerine, particularly .in times of Many compounds are well known which are war. Furthermore, this product which replaced more or less useful for the above purposes, but glycerine is easily obtainable in a form-that may ,0 nevertheless intensive efforts are being made to be readily converted into a true'sulphonate and i find compounds with moredesirable characterthis adds to thestability of the final material istics and/or that can be produced at less cost. without involving the diiflculty encountered in Among the known compounds that are useful as forming a true sulphonate from glycerine. i wetting agents, detergents and the like, are a The material that is used in place of glycerine l series of compounds which consist of glycerine, is beta methyl glycerine monochlorhydrin, which "one hydroxy group of which has been replaced by may be derived from isobutylene, which in turn a sulphate group,' and another hydroxy group of may come from petroleum. It is well known that which has been'replaced by a fatty acid radical beta methyl glycerine may be made from isoconnected to the glycerine molecule through an butylene, the product being converted, in the Q0 ester linkage. course of its treatment, into beta methyl glyce'r- Compounds of this generaltype are described ine monochlorhydrin, which is then converted in Patent 2,023,387, granted'to Benjamin R. Harinto beta methyl glycerine. By simply stopping ris on December 3, 1935, and in applications for the process at the point at'which the product is patents in the United States by Fred Weaver in the form of the monochlorhydrin, the mate- Muncie, filed June 27, 1935, and bearing Serial rial to be-used according to the present inven- 5 Numbers 28,711 and-28,712, now Patents Nos. tion is obtained. I 2,130,361 and 2,130,362, respectively, issued Sep- By combining with this material a fatty acid tember 20, 1938. Other compounds which are or 'a mixture of fatty acids, and aflixing to it a generally similar except that they are true sulsulphonate radical, a composition of the folno phonates instead of sulphates are also known, lowing structural formula is obtained: having been described, for example; in United States Patent 2,006,309, granted to- Charles c. 01110001 Clark on June 25, 1935. 0H.' -0H According to the present invention, a new H'SOlM type of compound is provided which is gen- '35 erally similar to the type of compounds men- In this formula OOCR indicates a fatty acid tioned above, but which differs somewhat in radical which may be either saturated or units constitution and properties and possesses the saturated, and preferably has between 5 and 21' particular advantage of being mp y and easily carbon atoms in it, and M represents any suitmaterials. monium, triethanolammonium, calcium, or a In the case of the known compounds menmetaL glycerme is an essential mgtedient' There'is some possibility that the sulphonate, Glycenne, however, is a relatively expensive raw hydmxy and fatty acid radicals may not always miter 1a] f i a gffig gz gg gii z attach to the beta methyl glycerine' molecule in a m figgfi fi underessuch the same relative positions as those in which they are now shown, but may interchange their 'cumstances" it is ig i' :3 if positions with'one another To indicate this in of glycerine be avo e e pa on men one I W .EiiiiEE-ffi 233i;z.ititiifafii iiiiiilli n dric ale 0 su ars, or e e, e su .s

therefor, but tins has not proved to he been attached in ary positions, with the very satisfactory because most of these comunderstanding that the obviously possible variapounds are either too expensive ordonot functions thereof are within the scope of this inven- "3 tion as well as glycerine. I 1 tion. v I u acid.

The preferred method of making the new type of composition consists in reacting beta. methyl glycerine monochlorhydrin with an'aqueous solution of a suitable sulphite, such as sodium sulphite or ammonium sulphite. This results in a salt of dihydroxy methyl propane sulphonic acid, which product may be reacted with a fatty acid or a mixture of fatty acids in a reaction vessel equipped to facilitate the removal of water formed during the reaction. The best results have been obtained by heating these latter reactants, with agitation, at 175 C. to 225 C. for a period ranging from 4 to 15 hours. The progress of the reaction is assisted by reducing the pressure so as to remove as much of the water as possible during the later stages of the reaction. I

Alternatively, the sodium salt of dihydroxy methyl propane sulphonic acid may be formed as describedlabove or by any other method and finally converted into the ultimate product by reaction with a fatty acid halide. In this case, the reaction takes place at a somewhat lower temperature, namely, from 75 C. to 125 C.

Preferably, the remaining halogen acid willbe neutralized before any attempt is made to isolate I the final product.

Still another way of making the same type'of product is by forming a soluble salt of a halogen hydroxy methyl propane sulphonic acid by partially sulphonating a beta methyl glycerine dichlorhydrin and thereafter reacting the neutralized sulphonate with an alkali salt of a fatty The products made by the methods given are not entirely pure, and usually contain a considerable quantity-of inorganic or organic sulphates or. chlorides formed by the neutralization of excess acid or acid freed in the reactions, but they may be used for many of the purposes for which they are intended in the state in which they are prepared. Further purification maybe effected by crystallization of the impure product from alcohol.

As a specific example of one method of forming the new product, the following may be cited: To a boiling solution of 63 parts by weight (0.5 mole) of sodium sulphite in 222 parts of water, there was added dropwise 62.3 parts by weight (0.5 mole) of beta methyl glycerine alpha chlorhydrin. maintained sufficiently high to boil off water for a period of one hour, and the sodium salt of beta methyl-glycerine alpha sulphonic acid (sodium 1, 2 dihydroxy, 2 methyl propane, 3 sulphonate) resulted. This compound was heated with 102 parts by weight of.-cocoanut oil fatty acid for four hours at:- 200 C., agitation being maintained during' the entire period. The water evolved was allowed to escape and at the end of the reaction the product was purified by dis-' solving it in hot ethyl alcohol, filtering, and

crystallizing from' the filtrate. A nearly white, crystalline product resulted.

As a second example, 52 parts by weight (0.23

mole) of cocoanut oil fatty acid chloride was added to 40.5 parts by weight (0.25 mole) of the dry sodium salt of beta methyl glycerine alphasulphonic acid and the mixture heated at 100 C. to 120 C. with agitation for eight hours. At the end of this time the product was neutralized with caustic soda and purified as in the first example.

A foam test was made on samples of the material :produced by each of the methods mensoap treating equipment.

desirable.

The temperature of the mixture was tioned in the foregoing paragraph and it was found that 50 cubic centimeters of a 1% solution of the product, when placed in a 500 cc. graduated cylinder of 5 cm. diameter and shaken 20 times would produce a foam that reached the 4'75 cc. mark. Under similar conditions the sodium salt of a mono cocoanut fatty acid ester of glycerine mono sulphuric acid ester containing around 60% of sodium sulphate gave 450 cc. of foam.

A wetting test was also conducted by placing a piece of unwashed filter cloth in 100 cc. of a 1% aqueous solution of the new materialin a 250 cc. beaker. The piece of filter cloth was carefully dropped into the liquid so as to lie flatly on the surface of the solution. At the end of 18 seconds the cloth was completelywet and sank to the bottom. Under similar conditions the glycerine product mentioned above sank in about the'same time.

As has been said, the new materials may be used for deterging andwetting and for numerous purposes. They may be formed into beads, bars, flakes, chips, powders, or any other forms in which soap is ordinarily found, by the usual This is important. particularly, the ability of the product to form beads and bars, for by no means all sulphated or sulphonated materials can be prepared in these forms and the forms have, by extensive use in the soap industry, proved themselves to be highly In addition, emulsions may be made by incorporating the new materials in mixtures of oleaginous and aqueousmaterials, with, of course, sufficient agitation and other treatment to disperse one of the phases into the other.

We claim:

1. A a new composition of matter, a chemical compound consisting of beta methyl glycerine, one'hydroxy group of which has been esterified by a long-chain fatty acid and another hydroxy group of which has been replaced by a sulphonate radical.

2. As a new composition of matter, a chemical compound of the following formula:

CHzOO C R CHzSOaM in'which R is an alkyl radical having from 4 to 20 carbon atoms, and M is a cation of the group consisting of sodium, potassium, calcium, ammonium and trietl'ranolammonium.

3. As a new composition of matter, a chemical compound formed'by reacting upon beta methyl glycerine monochlorhydrin with sodium sulphite and condensing the resultant product with a long chain fatty acid.

4. A process of forming a chemical compound that comprises reacting upon beta. methyl glycerine monochlorhydrin with sodium sulphite and condensing the resultant product with a I long chain fatty acid.

5. A process as described in claim 4 in which the condensation is performed at a temperature of 175" C. to 225 C. and under sub-atmospheric pressure.

6. A process of forming a new chemical compound that comprises converting beta methyl glycerine monochlorhydrin into a salt of dihydroxy methyl propane sulphonic acid and condensing the-said sulphonic acid salt with a long chain i'atty'acid halide.

2,204,4aa l. A process of forming a chemical compound that comprises converting beta methyl glycerine dichlo'rhydrin into 'a. soluble salt of a halogen hydroxy methyl propane sulphonicacid and condensing said sulphonic acid salt with an ,alkali metal salt of a long chain fatty acid.

'8. A process as described in claim 4 in which the final product is purified by crystallization from alcohol.

9. As a new composition of matter, a composi-V 11. As a new composition of matter, a chemical v compound as described in claim 1 in the form of 12'. As a new composition of matter, a mixture of compounds of the formula:

' h cmooca euro-on v HlSOlM in which OCR represents acyl radicalsof cocoanut oil fatty acids, and M is a cation of the group consisting of sodium,- potassium, calcium, ammonium, and triethanolammon'ium.-v

13. As, a new composition of matter, a mixture of chemical compounds consisting of beta methyl glycerine, onehydroxy group of which has been esterifled by a cocoanut fatty acid and another hydroxy group of which has been replaced by a sulphonate radical. I

FRED WEAVER MUNCIE.

KENNETH L. RUSSELL. 

